Classifications

• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
  • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
  • H10K30/80—Constructional details
  • H10K30/88—Passivation; Containers; Encapsulations
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
  • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
  • H10K71/20—Changing the shape of the active layer in the devices, e.g. patterning
  • H10K71/231—Changing the shape of the active layer in the devices, e.g. patterning by etching of existing layers
  • H10K71/233—Changing the shape of the active layer in the devices, e.g. patterning by etching of existing layers by photolithographic etching
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
  • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
  • H10K30/10—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising heterojunctions between organic semiconductors and inorganic semiconductors
  • H10K30/15—Sensitised wide-bandgap semiconductor devices, e.g. dye-sensitised TiO2
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
  • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
  • H10K30/80—Constructional details
  • H10K30/81—Electrodes
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
  • H10K39/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic radiation-sensitive element covered by group H10K30/00
  • H10K39/30—Devices controlled by radiation
  • H10K39/32—Organic image sensors
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
  • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
  • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
  • H10K85/10—Organic polymers or oligomers
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
  • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
  • H10K85/10—Organic polymers or oligomers
  • H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
  • H10K85/113—Heteroaromatic compounds comprising sulfur or selene, e.g. polythiophene
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
  • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
  • H10K85/20—Carbon compounds, e.g. carbon nanotubes or fullerenes
  • H10K85/211—Fullerenes, e.g. C60
  • H10K85/215—Fullerenes, e.g. C60 comprising substituents, e.g. PCBM
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
  • H10K2102/00—Constructional details relating to the organic devices covered by this subclass
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
  • Y02E10/00—Energy generation through renewable energy sources
  • Y02E10/50—Photovoltaic [PV] energy
  • Y02E10/549—Organic PV cells

Definitions

• Optoelectronic device comprising an active organic layer with improved performance and its manufacturing method
• the present description relates generally to optoelectronic devices comprising optical sensors with organic photodiodes or display pixels with organic light-emitting diodes and their manufacturing methods.
• the manufacture of an organic optoelectronic device generally comprises the successive formation of at least partially overlapping elements, at least one of these elements being made of an organic material.
• a method of making an organic element includes depositing an organic layer and etching portions of the organic layer to delimit the organic element.
• An organic optoelectronic device generally comprises an active organic layer which is the area of the optoelectronic device in which the majority of the radiation of interest is captured by the optoelectronic device or from which the majority of the radiation of interest is emitted by the device optoelectronics.
• a drawback is that steps in the method for manufacturing the optoelectronic device, in particular the steps of etching the active layer, can lead to deterioration of the active layer and therefore to a reduction in the performance of the optoelectronic device.
• An object of one embodiment is to prevent deterioration of the active layer during the manufacture of the optoelectronic device.
• An object of one embodiment is the manufacture of an optoelectronic device with improved performance.
• One embodiment provides for a method of manufacturing an optoelectronic device comprising the following successive steps:
• the formation of the first opening and / or of the second opening is carried out by reactive ion etching.
• step d) comprises the application of a mask against the first layer interface, said mask comprising a third opening, the first opening being etched in the extension of the third opening.
• step d) comprises depositing a layer of a photosensitive resin on the first interface layer and the formation of a third opening in the layer of photosensitive resin, the first opening being engraved in the extension of the third opening.
• the method comprises, between steps a) and b), the formation of a block of photosensitive resin facing the second electrically conductive pad, said block comprising a top and sidewalls, and, after step c), the stack comprising the active organic layer and the first interface layer covers in particular the top of said block and does not completely cover the sidewalls, the method comprising in step d) the removal of said block.
• One embodiment also provides for an optoelectronic device comprising:
• the first interface layer and / or the second interface layer comprise at least one compound chosen from the group consisting of:
• the first interface layer and the second interface layer are made of different materials.
• the first and second conductive pads comprise at least one compound chosen from the group consisting of:
• the active organic layer comprises a P-type semiconductor polymer and an N-type semiconductor material
• the P-type semiconductor polymer being poly (3-hexylthiophene) (P3HT)
• P3HT poly [N - 9 '-heptadecanyl-2, 7-carbazole-alt-5, 5- (4, 7-di-2-thienyl-2', l ', 3' -benzothiadiazole)]
• PCDTBT poly [(4 , 8-bis- (2- ethylhexyloxy) -benzo [1, 2-b; 4, 5-b '] dithiophene) -2, 6-diyl- alt- (4- (2-ethylhexanoyl) -thieno [3, 4-b] thiophene)) -2, 6-diyl]
• PBDTTT-C poly [2-methoxy-5- (2-ethyl-hexyloxy) - 1, 4-phenylene-
• PCPDTBT 4, 7 (2, 1, 3-benzothiadiazole)]
• N-type semiconductor material being a fullerene, [6, 6] -phenyl-C61-butanoate ([60] PCBM), [ Methyl 6, 6] -phenyl-C71- butanoate ([70] PCBM), perylene diimide, zinc oxide or nanocrystals allowing the formation of quantum dots.
• the device is suitable for emitting or capturing electromagnetic radiation, the active organic layer being the layer of the optoelectronic device in which the majority of the electromagnetic radiation is captured by the optoelectronic device or of which the majority electromagnetic radiation is emitted by the optoelectronic device.
• FIG. 1 is a partial and schematic sectional view of the structure obtained in a step of an example of a method of manufacturing an optoelectronic device comprising an organic active layer;
• FIG. 2 illustrates another step of the method
• FIG. 3 illustrates another step of the method
• FIG. 4 illustrates another step of the method
• FIG. 5 represents an image acquired by an optoelectronic device illustrating first defects of the active layer of the optoelectronic device
• FIG. 6 represents an image acquired by an optoelectronic device illustrating second defects of the active layer of the optoelectronic device
• FIG. 7 is a partial and schematic sectional view of the structure obtained in a step of an embodiment of a method of manufacturing an optoelectronic device comprising an organic active layer;
• FIG. 8 illustrates another step of the method
• FIG. 9 illustrates another step of the method
• FIG. 10 illustrates another step of the method
• FIG. 11 illustrates another step of the method
• Figure 12 is a sectional view, partial and schematic, of the structure obtained in a step of another embodiment of a method of manufacturing an optoelectronic device comprising an organic active layer;
• FIG. 13 illustrates another step of the method
• FIG. 14 illustrates another step of the method
• FIG. 15 illustrates another step of the method
• FIG. 16 illustrates another step of the method
• FIG. 17 is a top view, partial and schematic, of an embodiment of an organic photodiode
• Figure 18 is a sectional view, partial and schematic, of the structure obtained in a step of another embodiment of a method of manufacturing a optoelectronic device comprising an organic active layer;
• FIG. 19 illustrates another step of the method
• FIG. 20 illustrates another step of the method
• FIG. 21 illustrates another step of the method
• FIG. 22 illustrates another step of the method
• FIG. 23 illustrates another step of the method
• FIG. 24 illustrates another step of the method.
• the terms “insulator” and “conductor” respectively mean “electrically insulating” and “electrically conductive”.
• in contact with means “in mechanical contact with”.
• the term “radiation of interest” refers to the radiation that it is desired to capture or emit by an optoelectronic device.
• the radiation of interest can comprise the visible spectrum and the near infrared spectrum, that is to say the wavelengths between 400 nm and 1700 nm, more precisely from 400 nm to 700 nm for the visible spectrum and from 700 nm to 1700 nm for near infrared.
• the transmittance of a layer to radiation is the ratio of the intensity of the radiation leaving the layer to the intensity of the radiation entering the layer, the rays of the incoming radiation being perpendicular to the layer.
• a layer or a film is said to be opaque to radiation when the transmittance of the radiation through the layer or the film is less than 10%.
• a layer or a film is said to be transparent to radiation when the transmittance of the radiation through the layer or the film is greater than 10%.
• Figures 1 to 4 are sectional views, partial and schematic, of structures obtained in successive steps of an example of a method of manufacturing an optoelectronic device 5 comprising optoelectronic components.
• Figure 1 shows the structure obtained after the following steps: providing a support 10 comprising an upper face 12; - Forming first and second conductive pads 14, 15 on the face 12 of the support 10;
• FIG. 2 shows the structure obtained after the formation of an etching mask 20 on the active layer 18.
• the etching mask 20 is a rigid mechanical part which is applied against the active layer 18.
• the etching mask 20 is obtained by depositing a layer of photosensitive resin 22 on the active layer 18, and forming openings 24 in the photosensitive layer 22, by photolithography techniques, to expose the organic layer 18 at the level of the second pads 15.
• the etching mask 20 is obtained by depositing blocks of resin directly at the desired locations on the active layer 18, for example by inkjet printing, heliography , serigraphy, flexography or nanoimprint. In this case, there is no photolithography step.
• FIG. 3 shows the structure obtained after the etching of openings 26 in the active layer 18 followed by the removal of the etching mask 20.
• the openings 26 are located in the extension of the openings 24 and expose the second pads 15. As this is illustrated in FIG. 3, the openings 26 delimit two active zones 28 each associated with an optoelectronic component, each active zone 28 covering one of the first pads 14.
• FIG. 4 represents the structure obtained after the formation, for each optoelectronic component, of a interface layer 30 covering the active zone 28 and the second pad 15. Two optoelectronic components PH are thus obtained.
• a film of the material constituting the interface layers 30 can be deposited on the whole of the structure shown in FIG. 3 and the delimitation of the interface layers 30 can be obtained by etching, by using a mask. etching which can be formed by steps of photolithography on a layer of photosensitive resin deposited on the entire film or by depositing blocks of resin directly at the desired locations on the film, for example by inkjet printing, heliography, screen printing, flexography, or nano printing.
• the interface layers 30 can be deposited directly at the desired locations, for example by inkjet printing, heliography, screen printing, flexography, or nanoprinting.
• the performances of the active zone 28 of each optoelectronic component PH depend in particular on the surface condition of the active zone 28 in contact with the interface layer 30. In general, it is desirable that the surface of the zone active 28 in contact with the interface layer 30 exhibits the fewest possible defects, the defects possibly corresponding to surface roughness, in particular scratches, or to undesirable deposits (particles, contamination, etc.) interposed between the active zone 28 and the interface layer 30.
• a drawback is that the steps of the manufacturing method described above can lead to the production of active zones 28 having defects.
• the contact of the etching mask 20 with the active layer 18, in particular during the placement of the engraving mask 20, may cause the formation of surface defects of the active layer 18. These defects can in particular correspond to scratches which may extend over the entire thickness of the active layer 18. These defects result in a local reduction in the performance of the active layer 18, for example by a higher leakage current or a lower sensitivity.
• FIG. 5 represents an image obtained in the case where the optoelectronic device 5 corresponds to an image sensor used for the acquisition of fingerprints and the engraving mask 20 is a rigid mechanical part applied against the active layer 18.
• saturated image pixels 32 can be observed, corresponding to white image pixels in FIG. 5, due to surface defects of the active layer 18 resulting from the application of the etching mask 20. , in particular a local short-circuit between the interface layer 30 and the conductive pad 14 of the photodiode forming the image pixel.
• a step of removing the etching mask 20 must be carried out after the formation of the openings 26 in the active layer 18, for example by dipping the structure comprising the etching mask 20 in a chemical bath.
• the removal of the etching mask 20 must not lead to etching of the active layer 18, which can lead to constraints as to the composition of the chemical bath. Therefore, it can be difficult to ensure the complete removal of the resin etching mask, which can lead to the presence of unwanted residues on the active layer 18.
• FIG. 6 represents an image obtained in the case where the optoelectronic device 5 corresponds to an image sensor and where the etching mask 20 is made of resin.
• the image obtained comprises traces 34 reflecting the presence of residues on the active layer 18.
• Figures 7 to 11 are sectional views, partial and schematic, of structures obtained in successive steps of an embodiment of a method of manufacturing an optoelectronic device 35.
• FIG. 7 shows the structure obtained after the following steps:
• a support 40 comprising an upper face 42;
• the layers 46, 47 and 48 can each be deposited by liquid. These may be processes of the spin coating, spray coating, heliography, slot-die coating, blade coating, flexography, screen printing, or dipping (in English dip coating, in particular for layer 46). As a variant, the layers 47 and 48 can be deposited by sputtering or by evaporation. Depending on the deposition process put in practice, a step of drying the deposited materials can be provided.
• the support 40 may correspond to an integrated circuit comprising a semiconductor substrate, for example in monocrystalline silicon, in which and on which are formed the insulated gate field effect transistors, also called MOS transistors. , for example N-channel and P-channel MOS transistors, and a stack of insulating layers covering the substrate and the transistors, conductive tracks and conductive vias being formed in the stack to electrically connect the transistors and the pads.
• the integrated circuit 40 may have a thickness between 100 ⁇ m and 775 ⁇ m, preferably between 200 ⁇ m and 400 ⁇ m.
• the support 40 can be made of a dielectric material.
• the support 40 is, for example, a rigid support, in particular of glass or a flexible support, for example of polymer or of a metallic material.
• polymers are polyethylene naphthalene (PEN), polyethylene terephthalate (PET), polyimide (PI), and polyetheretherketone (PEEK).
• the thickness of the support 40 is then, for example, between 20 ⁇ m and 1 cm, for example approximately 125 ⁇ m. In the case where the radiation of interest emitted or picked up by the optoelectronic components must pass through the support 40, the latter may be transparent.
• the material making up the conductive pads 44, 45 is chosen from the group comprising:
• a conductive oxide such as tungsten oxide (W0 3) , nickel oxide (NiO), vanadium oxide (V2O5), or molybdenum oxide (M0O3), in particular a transparent conductive oxide ( TCO, acronym for Transparent Conductive Oxide), in particular indium oxide doped with tin (ITO, acronym English for Indium Tin Oxide), an oxide of zinc and aluminum (AZO, acronym for Aluminum Zinc Oxide), an oxide of gallium and zinc (GZO, English acronym for Gallium Zinc Oxide), a multilayer structure ITO / Ag / ITO, an ITO / Mo / ITO multilayer structure, an AZO / Ag / AZO multilayer structure or a ZnO / Ag / ZnO multilayer structure;
• TiN titanium nitride
• a metal or a metal alloy for example silver (Ag), gold (Au), lead (Pb), palladium (Pd), copper (Cu), nickel (Ni), tungsten (W), molybdenum (Mo), aluminum (Al), chromium (Cr), or an alloy of magnesium and silver (MgAg);
• PEDOT PEDOT: PSS polymer, which is a mixture of poly (3, 4) -ethylenedioxythiophene and sodium polystyrene sulfonate, or a polyaniline;
• the pads 44, 45 may be transparent to the radiation of interest.
• the active layer 47 comprises at least one organic material and can comprise a stack or a mixture of several organic materials.
• the active layer 47 can comprise a mixture of an electron donor polymer and an electron acceptor molecule.
• the thickness of the active layer 47 can be between 50 nm and 2 ⁇ m, for example of the order of 300 nm.
• the active layer 47 can comprise small molecules, oligomers or polymers. They can be organic or inorganic materials.
• the active layer 47 may comprise an ambipolar semiconductor material, or a mixture of an N-type semiconductor material and a P-type semiconductor material, for example in the form of superimposed layers or of an intimate mixture at the nanoscale so to form a heterojunction by volume.
• P-type semiconductor polymers suitable for producing the active layer 47 are poly (3-hexylthiophene) (P3HT), poly [N-9 ′ -heptadecanyl-
• PCDTBT poly [(4, 8-bis- ( 2- ethylhexyloxy) -benzo [1, 2-b; 4, 5-b '] dithiophene) -2, 6-diyl- alt- (4- (2-ethylhexanoyl) -thieno [3, 4-b] thiophene) ) -2, 6-diyl]
• PBDTTT-C poly [2-methoxy-5- (2-ethyl-hexyloxy) - 1, 4-phenylene-vinylene] (MEH-PPV) or poly [2, 6- (4, 4-bis- (2-ethylhexyl) -4H-cyclopenta [2, 1-b; 3, 4-b '] dithiophene) -alt-
• N-type semiconductor materials suitable for producing the active layer 47 are fullerenes, in particular C60, methyl [6, 6] -phenyl-C61-butanoate ([60] PCBM), Methyl [6, 6] -phenyl-C71-butanoate ([70] PCBM), perylene diimide, zinc oxide (ZnO) or nanocrystals allowing the formation of quantum dots (in English quantum dots).
• the interface layer 48 may correspond to an electron injecting layer or to an injecting layer of holes.
• the output work of the interface layer 48 is suitable for blocking, collecting or injecting holes and / or electrons depending on whether this interface layer acts as a cathode or an anode. More precisely, when the interface layer 48 acts as an anode, it corresponds to a hole injecting and electron blocking layer. The output work of the interface layer 48 is then greater than or equal to 4.5 eV, preferably greater than or equal to 4.8 eV. When the interface layer 48 acts as a cathode, it corresponds to an electron injecting and hole blocking layer. The output work of the interface layer 48 is then less than or equal to 4.5 eV, preferably less than or equal to 4.2 eV.
• the interface layer 48 is transparent to the radiation of interest.
• the thickness of the interface layer 48 can be between 10 nm and 2 ⁇ m, for example of the order of 300 nm.
• the material making up the interface layer 48 is chosen from the group comprising:
• a metal oxide in particular a titanium oxide or a zinc oxide
• a host / molecular dopant system in particular the products marketed by the company Novaled under the names NET-5 / NDN-1 or NET-8 / MDN-26;
• PEDOT Tosylate polymer which is a mixture of poly (3,4) - ethylenedioxythiophene and of tosylate;
• PEI polyethyleneimine
• PEIE ethoxylated polyethyleneimine
• polyelectrolyte for example poly [9, 9-bis (3 '- (N, N-dimethylamino) propyl) -2, 7-fluorene-alt-2, 7- (9, 9-dioctyfluorene)] (PFN ), poly [3- (6-trimethylammoniumhexyl) thiophene] (P3TMAHT) or poly [9,9- bis (2-ethylhexyl) fluorene] -b-poly [3- (6-trimethylammoniumhexyl] thiophene (PF2 / 6-b-P3TMAHT); and
• the material making up the interface layer 48 can be chosen from the group comprising:
• a doped conductive or semiconductor polymer in particular the materials sold under the names Plexcore OC RG-1100, Plexcore OC RG-1200 by the company Sigma-Aldrich, the PEDOT polymer: PSS, or a polyaniline;
• a host / molecular dopant system in particular the products marketed by the company Novaled under the names NHT-5 / NDP-2 or NHT-18 / NDP-9;
• polyelectrolyte for example Nafion
• a metal oxide for example a molybdenum oxide, an oxide of vanadium, ITO, or an oxide of nickel
• FIG. 8 represents the structure obtained after the formation of an etching mask 50 on the interface layer 48.
• the etching mask 50 is obtained by depositing a layer of photosensitive resin 52 on the interface layer 48, and the formation of openings 54 in the photosensitive layer 52, by photolithography techniques, to expose the interface layer 48 in particular at the level of the second pads 45.
• the mask etching 50 is obtained by depositing resin blocks directly at the desired locations on the interface layer 48, for example by inkjet printing, heliography, screen printing, flexography, nano-printing. In this case, there is no photolithography step.
• the etching mask 50 is a rigid mechanical part comprising the openings 54 and which is applied against the interface layer 48.
• FIG. 9 represents the structure obtained after the etching of openings 56 in the interface layer 48 in the extension of the openings 54 and the etching of openings 58 in the active layer 47 in the extension of the openings 56, in particular to expose the second pads 45.
• the openings 56, 58 delimit two active zones 60 each associated with an optoelectronic component, each active zone 60 covering the associated first pad 44.
• Each etching can be a reactive ionic etching (RIE, acronym for Reactive-Ion Etching) or a chemical etching.
• RIE reactive ionic etching
• FIG. 10 represents the structure obtained after the removal of the etching mask 50.
• the removal of the etching mask 50 can be obtained by any stripping process, for example by soaking the structure comprising the etching mask 50 in a chemical bath or by RIE etching.
• FIG. 11 represents the structure obtained after the formation, for each active zone 60, of a conductive connecting element 62 at least partially covering the interface layer 48 and covering the associated second pad 45, preferably in contact. of the interface layer 48 and in contact with the interface layer 48 covering the second pad 45.
• the connecting element 62 can be made from one of the conductive materials from the list of materials mentioned above for the layer d interface 48.
• the connecting element 62 may be of the same material as the interface layer 48 or of a material different from that of the interface. interface layer 48.
• the connecting element 62 preferably completely covers the interface layer 48.
• the interface layer 48 can be transparent to the radiation of interest and the connecting element 62 may be opaque to the radiation of interest, in particular when the interface layer 48 is conductive and the connecting element 62 only partially covers the interface layer 48.
• the maximum thickness of the connecting element 62 can be between 10 nm and 2 ⁇ m.
• the process for forming the connecting elements 62 may correspond to a so-called additive process, for example by direct printing of a fluid or viscous composition comprising the material making up the connection tracks at the desired locations, for example by inkjet printing, heliography, screen printing, flexography, spray coating (in English spray coating), depositing of drops (in English drop-casting), or nanoimpression.
• the method for forming the connecting elements 62 may correspond to a so-called subtractive process, in which the material making up the connection tracks is deposited over the entire structure.
• the deposition over the entire structure can be carried out, for example, by liquid, by cathode sputtering or by evaporation. They may in particular be processes of the spin coating, spray coating, heliography, slot-die coating, blade coating, flexography or screen printing type. According to the process deposition implemented, a step of drying the deposited materials can be provided.
• the step of delimiting the active zones 60 uses an etching mask 50 which is applied against the interface layer 48 and not against the active layer 47. Therefore, the surface of the active layer 47 in contact with interface layer 48 is not degraded by etching mask 50. In addition, removal of etching mask 50 cannot result in the presence of residues in contact with the interface between the etching. active layer 47 and interface layer 48. In addition, when the etching mask 50 is made of photosensitive resin, there are fewer constraints as to the choice of the treatment implemented for the removal of the etching mask 50 because of lower sensitivity of interface layer 48.
• Figures 12 to 16 are sectional views, partial and schematic, of structures obtained in successive steps of another embodiment of a method of manufacturing the optoelectronic device 35.
• FIG. 12 represents the structure obtained after the step of forming the conductive pads 44, 45 on the face 42 of the support 40 and of the interface layers 46 on the conductive pads 44, 45, only one conductive pad 44 and a conductive pad 45 being shown in Figures 12 to 16.
• FIG. 13 represents the structure obtained after a step of forming a sacrificial block 64 on each second pad 45, a single block 64 being represented in FIG. 13.
• Each sacrificial block 64 is preferably made of a photosensitive resin.
• the sacrificial blocks 64 can be formed by photolithography steps.
• each sacrificial block 64 may have a flared shape away from the stud 45 on which it rests or a so-called profile. in a cap, that is to say having a vertex of larger dimensions than the base in contact with the pad 45.
• such a shape can be obtained in particular by providing, during the photolithography steps, a step of hardening of the surface of the photosensitive layer used to form the blocks 64, for example by immersing the resin layer in an aromatic solvent, such as chlorobenzene
• a shape can be obtained during the step of development of the resin layer, the resin being chosen to have a development rate which varies in the direction perpendicular to the resin layer, the resin layer being more resistant to development on the side of its free upper face.
• the dimensions of the base of the block 64 are greater than the pad 45 so as to ensure that the block 64 covers the whole of the pad 45.
• FIG. 14 represents the structure obtained after a step of depositing the active layer 47 and the interface layer 48 on the entire structure shown in FIG. 13.
• the thickness of the part of each sacrificial block 64 lying on the interface layer 46 is preferably greater than the sum of the thicknesses of the active layer 47 and the interface layer 48.
• the stack of the active layer 47 and the interface layer 48 extends on the pads 44, 45, on the face 42 of the support 40 between the pads 44, 45 and on the upper face of each sacrificial block 64.
• the method of forming the stack is preferably a directional deposition method so that , due to the flared shape of the block 64 which is wider at its top than at its base, the stack does not deposit on at least part of the side walls of the block 64.
• FIG. 15 represents the structure obtained after a step of removing the sacrificial blocks 64. According to a mode of embodiment, this is achieved by soaking the structure shown in Figure 14 in a bath containing a solvent which dissolves the sacrificial blocks 64 selectively without dissolving the interface layer 48. The formation of openings 56 in the layer is thus obtained. interface 48 and openings 58 in the active layer 47 delimiting the active areas 60.
• FIG. 16 represents the structure obtained after the formation, for each active zone 60, of the connecting element 62 partially covering the interface layer 48 and covering the associated second pad 45, preferably in contact with the layer. interface 48 and the interface layer 46 covering the second pad 45.
• Figure 17 is a top view with transparency, partial and schematic, of an embodiment of component 35 corresponding to an organic photodiode.
• the stack comprising the active zone 60 and the interface layer 48 has, in top view, a circular shape.
• Figures 18 to 24 are sectional views, partial and schematic, of structures obtained in successive steps of an embodiment of a method of manufacturing an optoelectronic device comprising a sensor with organic photodiodes and MOS transistors.
• Figure 18 is a sectional view, partial and schematic, of an example of integrated circuit 68 comprising a matrix of MOS transistors, six read circuits 70 with MOS transistors being represented schematically by rectangles in the figures 18 to 24.
• the integrated circuit 68 is produced by conventional techniques in microelectronics. Conductive pads are formed on the surface of the integrated circuit 68. Among these conductive pads, there are pads 72 formed.
• a zone 74 of the integrated circuit 68 which will be used as lower electrodes for the organic photodiodes, and, outside the zone 74, for example at the periphery of the circuit 68, of the pads 76 which will be used for the polarization of the upper electrode of the photodiodes, a single pad 76 being shown in Figures 18 to 24, and pads 78 which will be used for the polarization of the integrated circuit 68, a single pad 78 being shown in Figures 18 to 24.
• the integrated circuit 68 may comprise a semiconductor substrate, for example in monocrystalline silicon, in which and on which are formed the insulated gate field effect transistors, also called MOS transistors, for example MOS transistors. N-channel and P-channel, and a stack of insulating layers covering the substrate and the read circuits 70, conductive tracks and conductive vias being formed in the stack to electrically connect the read circuits 70 and the pads 72, 76, 78.
• MOS transistors also called MOS transistors
• FIG. 19 represents the structure obtained after the formation on each pad 72 of an organic interface layer 80.
• the forming method used can furthermore result in the formation of the organic layer on the pads 76 and 78, this which is not shown in FIG. 19.
• the interface layer 80 can be made of cesium carbonate (CSCO 3 ), of metal oxide, in particular of zinc oxide (ZnO), or of a mixture of at least two of these compounds.
• the interface layer 80 may comprise a self-assembled monomolecular layer or a polymer, for example polyethyleneimine, ethoxylated polyethyleneimine, or poly [(9,9- bis (3 '- (N, N-dimethylamino) propyl) -2 , 7-fluorene) -alt-2, 7-
• the thickness of the interface layer 80 is preferably between 0.1 nm and 1 ⁇ m.
• Layer interface 80 can be grafted in a privileged way on the pads 72 (and possibly 76 and 78), which directly gives the structure shown in FIG. 19.
• the interface layer 80 can be deposited on the whole of the structure shown in Figure 18, and then be etched outside the pads 72 to give the result shown in Figure 19.
• the interface layer 80 can be deposited on the entire structure shown in FIG. 18, this layer having a very low lateral conductivity so that it is not necessary to remove it outside of the pads 72, 76, 78.
• FIG. 20 represents the structure obtained after the formation of an organic active layer 82 over the whole of the structure shown in FIG. 19 and in which the active zones of the photodiodes will be formed, in operation.
• the active layer 82 can have the same composition as the active layer 47.
• FIG. 21 represents the structure obtained after the deposition of an interface layer 84 on the active layer 82.
• the interface layer 84 can have the same composition as the interface layer 48.
• FIG. 22 represents the structure obtained after the deposition of a layer of photosensitive resin 86 on the interface layer 84, and the formation of openings 88 in the photosensitive layer 86, by photolithography techniques, only one opening 88 being shown in FIG. 22, to expose the interface layer 84 at the level of the pads 76.
• FIG. 23 represents the structure obtained after the etching of openings 90 in the interface layer 84 in the extension of the openings 88 of the photosensitive layer 86, and the etching of openings 92 in the active layer 82 in the extension of the openings 90 of the interface layer 84 to expose the pads 76.
• FIG. 24 represents the structure obtained after the removal of the photosensitive layer 86 and after the deposition, over the entire structure, of a tie layer 94.
• the tie layer 94 is in particular in contact with the pads 76 and may have the same composition as the connecting elements 62.
• the method may in particular comprise subsequent steps of etching the tie layer 94 and the formation of an encapsulation layer covering the entire structure.
• the structure comprises, in the zone 74, an array of organic photodiodes 96 forming an optical sensor, each photodiode 96 being defined by the portion of the organic layers 82, 84 facing one of the pads 72
• six organic photodiodes 96 are shown. In practice, this matrix is located directly above the read circuits 70 which, in operation can be used for controlling and reading the photodiodes 96.
• the layer 80 is shown discontinuous at the level of the photodiodes. 96 while the organic layers 82 and 84 are shown continuous at the photodiodes 96.
• the interface layer 80 may be continuous at the photodiodes 96.
• the thickness of the stack may be between 300 nm and 1 ⁇ m, preferably between 300 nm and 500 nm.

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• 2019
  • 2019-07-19 FR FR1908250A patent/FR3098982B1/fr active Active
• 2020
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  • 2020-07-16 JP JP2022503880A patent/JP2022542039A/ja active Pending
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